Insecticidal materials produced by the destructive distillation of gilsonite



Q a aae Patented Aug. 1, 1961 INSECTICIDAL MATERIALS PRODUCED BY THE DESTRUCTIVE DISTILLATION F GILSONITE Nathan W. Davis, 3474 S. 23rd St., Salt Lake City, Utah No Drawing. Original application Aug. '15, 1956, Ser.

No. 604,085. Divided and this application Sept. 21,

1959, Ser. No. 846,525

2 Claims. (Cl. 167-14) This invention relates to hydrocarbons obtained by destructive distillation of Gilsonite and to products made from the distillates.

It is an object of this invention to destructively distill Gilsonite and to obtain therefrom various fractions each of which are separate and distinct insofar as they have different physical and chemical properties.

It is a further object of this invention to use one or more of these fractions to obtain an insecticidal composition.

It is a still further object of this invention to one or more of these fractions in compounding a pai t composition.

A still further object of this invention is to use one of these distilled fractions in producing an elastomeric product.

Gilsonite is a black, brittle, lustrous mineral consisting of hydrocarbons, chiefly found in the Southwestern section of the United States, principally in Utah and Colorado.

DESTRUCTIVE DIST-ILLATION OF GILSONITE In a steel still directly heated by means of electric resistance units is placed 50 pounds of Gilsonite M.P.320 350 F. This still is connected to a water cooled condenser and the following fractions obtained at the temperature indicated. For the purpose of further reference in this specication, these fractions have been following numbers. Table of Gilsonite distillates using a 320 F. melt point Gilsonite [The following distillates are obtainable] given the Speiiic Gravity at 70 13.

Temperature, Color slightly brown cleangeddish brown More fractions are obtainable but they are not part of this invention.

EXAMPLE I A carbon silicate acid is obtained from the 16 fraction by treating as follows:

In a retort that will stand 600 pounds pressure, place:

1 gal. distillate, fraction 16 12 oz. xylene (dimethylbenzene) 2 oz. triethafiolamine (tlihydroxytriethylamine) 6 oz. silicon mix (finely ground silicon dioxide 100 mesh) Heat to 250 F. maintaining a pressure of 30 pounds per square inch with continual agitation for one hour.

The retort is then allowed to cool, maintaining the agitation, and when cool, 1 gallon of distilled water is added. This is then distilled and three fractions taken at 230-240 F., 260270 F. and 3lO-315 F., using a water cooled condenser. The last fraction, that is, the one boiling at 310-315 F. is a fluid brownish liquid having a specific gravity of .24 at 70 F., and is then diluted with mineral spirits solvent in the ratio of 1 part distillate to parts solvent. The following solvents have also proven satisfactory: Stoddalt Solvents manufactured by the Standard Oil Company and turpentine. This material has the following formula:

This is referred to in this application as Z It is a hydrocarbon silicon penetrating oil, a silicon carbonate or carboxy acetic acid.

Similar destructive distillation of coal or crude oil may be run and used in place of the 16th fraction from the destructive distillation of Gilsonite, after the addition of xylene triethanolamine and the silica and distilled, the fraction boiling at 260 F. for crude oil and 310 F. for coal can be used after dilution with mineral spirits.

A product is similarly obtained by treating the #6 fraction as follows:

Mix in a heated retort with agitation- 1 gal. of #6 fraction (an oily brown, black material having a specific gravity of 1.31 at 70 F.)

7 oz. triethanolamine (trihydroxytriethylamine) 1 lb. silicon mix (finely ground silicon dioxide mesh) 20 oz. xylene (dimethylbenzene) Mix and heat under pressure to 300 maintaining a pressure of 20 lbs.'per square inch wit continual agitation for one hour. Cool and add'l gal. of distilled water and 1 pt. turpentine. Heat with agitation to 256 F. and distill. An oily distillate having a specific gravity of .63 at 70 F. is obtained. This is a very toxic material and is used in the preparation of Med to below. This is heretofore referre to as the Z6 material. This material has the following formula:

(4H 4CO OH(2Si O2H O) EXAMPLE II.PAINT A black colloidal non-toxic paint for waterproofing and rust-proofing metal, wood, concrete etc., which is resistant to heat, acid and alkali and moisture can be applied by brushing, spraying or dipping is prepared as follows:

Mix and heat in an open vessel- 20 gal. petroleum solvent, such as mineral spirits or xylene 10 gal. boiled linseed 0'' 10 gal. turpentine, veood distilled or gum spirits of turpentine After heating to 100 F. slowly add lbs. pulverized -200 mesh Gilsonite, a pigment melting at 320- 350 F. This mixture is then heated to 150 F., then slowly add 4 gals. of varnish (PT 358 National Lead Company) 1 gal. Petronate 8 or 9 Sonneborn Sons Inc., New York, wetting agent.

2 qts. of a mixture of 1 part lead, 1 part cobalt and 2 parts manganese drier 1 pt. of the penetrating oil not diluted, obtained as outlined above (Z16) This mixture is heated until the mixture reaches 200 F., continuously mixing for 15 minutes and then allowed to cool. It is drawn off and sealed in containers. This produces approximately 55 gals. of paint.

EXAMPLE Ill-ALUMINUM PAINT An aluminum paint, slightly toxic, which is resistant to heat, acid, and alkali, as well as moisture, can be applied by spraying, brushing or dipping, is prepared as follows:

Mix in an open agitator 12 gal. boiled linseed oil gal. petroleum solvent, such as mineral spirits or xylene 6 gal. paint prepared as in Example II 10 gal. 50-50 coal resin and petroleum solvent, 50% ordinary coal resin 50% mineral spirits 3 gal. #30 aluminum pigment ground in oil 2 qts. Petronate 8 or 9 (wetting agent) (manufactured by Sonneborn Sons Inc. of New York) 2 qts. mixed drier (-1 part lead, 1 part cobalt, 2 parts manganese) 1 pt. carbon silicate acid prepared as set forth above in Example I (Z16) Mix thoroughly until all of the aluminum pigment is suspended, then draw off and seal in containers.

EXAMPLE IV.-INSECTICIDES The following composition is prepared by mixing in an ordinary agitator:

10 lbs. wheat bran (vehicle) 1 pt. corn syrup (bait) 2 lbs. Gilsonite Z6 (poison) 2 ozs. arsenic trioxide (optional) (poison) 2 ozs. benzaldehyde (attractant) This insecticide is especially effective on earwigs, cockroaches and silver fish.

EXAMPLE V.INSECTICIDES The following composition is prepared by mixing in an ordinary agitator.

Mix together with continuous agitation:

3 gal. kerosene (solvents) 2 gal. turpentine (solvents) 2 oz. oil of Pennyroyal (an essential oil) (attractant) 4 oz. creosol dip(poison) 6 oz. carbon-silicate acid Z6 prepared according to Example I given above before dilution with mineral spirits (poison) 1%. oz. chlordane (octa-chlor-hexahydro methanoindene) (poison) 3 oz. odormask M, D, or H, Polok and Schwars Inc. of

New York This is particularly effective for termites, ants, spiders and related insects.

EXAMPLE VI.ELASTOMER This process is adapted to the use of any parafiinic hydrocarbon, such as Gilsonite, elaterite (commonly known as Wurtzalite), Sunnyside hydrocarbons, Rozel asphalt, and also to bituminous coal. If bituminous coal is used as the basic material, the first step is slightly varied from the first step applicable when another hydrocarbon 'is used as the basic material.

4 STEPS IN THE PROCESS Step N0. 1

(A) For hydrocarbons other than bituminous coal.-

If a solid hydrocarbon other than coal is used as the base material, the hydrocarbon should be powdered. The first mass consists of 27 pounds or any multiple thereof, and based upon a 27 pound quantity, the materials are used in the following ratios:

20 pounds of any paraffinic hydrocarbon other than coal, such as powdered Gilsonite, elaterite (Wurtzalite), Sunnyside hydrocarbons, etc. or Rozel asphalt or other semi-liquid hydrocarbon.

7 pound of raw linseed oil, or hydrogenated cottonseed oil or any other acid base vegetable oil.

27 pounds This mass as combined is mixed thoroughly until smooth, at normal room temperature.

(B) If bituminous coal is used as the base material, the first step is as follows, using a mass of 27 pounds or any multiple thereof:

27 pounds These oils are processed by distillation by heating solids 'ortesgmi-solid hydrocarbons to the temperatures F. as indica This mass as combined is mixed thoroughly until smooth, at normal room temperature.

Step N0. 2

Add to the foregoing base mass as compounded in Step No. 1, one pound of an oily wax, preferably a substance known as Altawax (or any other oily Wax having the same chemical properties and reactions). A description of the process for making Altawax is indicated hereinafter. This wax should be added by mixing it with the base material described in Step No. 1.

Step No. 31

Add 1 /2 pounds of a sulfonated product obtained by treating out No. 2 from the distillation of Gilsonite as described above, which boils within the range of 330- 334 F. with sulfuric acid and then add 10% furfural and 5% oleic acid to of the sulfonated product. This is then distilled and a cut distilling at 340 F. to 590 F. The residue is the Altawax referred to above.

Step N0. 4

Add one-half pound of furfural which will aid polymerization and also one pound of zinc sulphate which will act as an accelerator of polymerization.

In lieu of zinc sulphate, at least one, of any number of other accelerators may be used to produce the same result, some of which are produced commercially under specified tradenames, such as: Santocure, Resinex, Silicon, Lumanall, Sulfurdioxide, Ethyleneglycol, Diethyleneglycol, Cresylic Acid, Naphthenic Acid, Sodium sulfonate, Santicizer 141, Peracetic Acid, Elastex 50 B, Carbonex, Bordol, Glycerine, or 'Oxalic Acid. Various other chemicals or commercial substances may be used which produce the same results.

Step N0. 5

When all of the substances indicated in Steps No. 1, 2, 3 and 4 have been combined, regardless of which substance is first added to the mixed mass of Step. No. 1, whether material described in Steps. No. 2, 3 or 4, the aggregate of all of these substances should be mixed thoroughly for approximately one hour at ordinary room temperature, not less than 40 F. nor in excess of 120 F.

Step N 0. 6

The aggregate so compounded and mixed is then subjected to slow heat. The temperature should be stepped up gradually until it reaches 200 F. within a period of two and one-half hours, during which time the compounded substances should be mixed at a moderate speed. The compounded substances should continue to be mixed at such speed for approximately 6 hours at 200 F. from the time when such temperature is first reached.

Step No. 7

The temperature is then gradually increased to 350 F. with an increase of pressure to 50 pounds, the mixing continuing during this increase in temperature. This mixing process at 50 pounds pressure and at 350 F. temperature continues for about 64 hours, unless the time is reduced by additional catalyst or booster in Step No. 4, as herein indicated.

To accelerate Step No. 7 and to reduce the time from 64 hours normally required in Step No. 7, any one or more of the catalysts or accelerators indicated in Step No. 4 may be added to the zinc sulphate in such quantity as the type of final product may be desired. The extent of reduction in time depends upon the combination and quantity of the accelerators used, however, at a slight sacrifice of quality.

Step No. 8

The temperature is then slowly decreased to 250 F. over a period of about 3 hours, during which time the mixing process continues.

Step N0. 9

Two pounds of Water and one pound of potassium sulfate for a plasticizer, are then added to the mass while the mixing process continues.

Step N0. 10

The temperature remains at 250 F. while the pressure is increased to 60 pounds by the addition of the water as indicated in Step. No. 9. This pressure and this temperature are maintained for about 3 hours while the mixing continues.

Step N0. 11

The pressure and temperature are then reduced slowly until pressure is entirely released and reduced to ze ro, and the temperature is reduced to 100 F., while mixing continues.

Step N0. 12

At this stage 2 pounds of sulphur (which should be at least 90% pure, if possible) should be added to the mass, unless the base material is Rozel asphalt in which event sulphur is not added. There should also be added at this stage of the processing 5 pounds of calcium oxide. These ingredients should be mixed into the mass for about 8 hours at a temperature of about 100 F., in an open con-' tainer under sunlight or ultra-violet rays or other light which produces the same general reaction as sunlight.

this phase of the process depends upon intensity of light and humidity. Suflicient moisture must be in the atmosphere to facilitate the curing process.

Step N0. 15

The cured mass is then ready for use. The material is also in condition for introduction of any rubber extenders or fillers, if desired, to give the elastomer a different degree of resiliency, or in order to reduce elasticity.

EXAMPLE VII.ORE REDUCTION PROCESS This process is adapted to a separation of complex mineral ores after the raw ore has been crushed and ground to the customary mesh common in conventional means of ore separation. The process is adaptable to all types of complex minerals including radioactive material, ferrous and nonferrous minerals.

STEPS IN THE PROCESS Step N0. 1

The complex ore as it comes from the ball mill or other grinding device at the required mesh is placed into an agitated heated tank for conditioning where the ore material is mixed with warm Water to a specific gravity of 60. Sulfuric acid is then mixed with the material in an amount equal to 1% of the lime content of the ore material while in the process of raising the temperature of the slurry to 200 F. Said temperature should not be obtained however until after completion of the second step.

Step N0. 2

During the process described above in Step. No. 1, when the lime has quit foaming introduce into the slurry the material previously described in this invention as Z16, in the amount equivalent to A of 1% of the sulfuric acid previously used. Then continue to mix or agitate the slurry for twenty minutes or until the temperature of the slurry obtains F. whichever event occurs first.

Step N0. 3

Now add hydrochloric acid in an amount equal to M4 of the sulfuric acid previously added. Continue to mix or agitate for thirty minutes or until the slurry reaches the temperature of 200 F., whichever occurs first.

Step N0. 4

Now introduce sodium bicarbonate into tank No. 2 in an amount by weight equivalent to twice the number of pounds of sulfuric acid by weight which has been previously added, then empty tank No. 1 into tank No. 2 and slowly agitate.

Step N0. 5

Then add potassium iodine in an amount equivalent of 2% of the sodium previously added.

Step N0. 6

If the ore headings contain carbon, use nitric acid in place of sulfuric acid in the preceding steps.

Step N0. 8

The aforesaid steps permit the sepaartion of various ores in the precipitant material contained in tank No. 2 or the soda tank as described in Step No. 4. The various 7 oreparticles are free and independent of each other and can be concentrated by conventional methods such as tabling or flotation.

Many minor changes could 'be made in the above process as described in this application. All such changes come within the scope of this invention. The important feature is the introduction of the Z16 material and its faculty to penertate through and cause separation at the microscopic seams or contact points between the various kinds of ore particles Which are commonly found united together in most ore material.

This application is a division of application Serial No. 604,085, filed Aug. 15, 1956.

What is claimed is:

1. An insecticidal composition comprising: a vehicle, a bait, an attractant and a poison obtained by adding to 1 gallon of the distillate boiling between 355 and 360 F.,

8 obtained by the destructive distillation of Gilsonite, adding 20 ounces of xylene, 7 ounces of triethylolamine and 1 pound of silicon dioxide, heating under pressure to 300 F. and cooling, adding 1 gallon distilled water and 1 pint of turpentine and then distilling the same and removing that fraction boiling above 256 F.

2. An insecticidal composition comprising: a solvent, an attractant, octa-chlor-hexahydro-rnethanoindene and a poison obtained by adding to 1 gallon of the distillate boiling between 355 and 360 F., obtained by the destructive distillation of Gilsonite, 20 ounces of Xylene, 7 ounces triethylolamine and 1 pound of silicon dioxide, heating under pressure to 300 F. and cooling, adding 1 gallon of distilled Water and 1 pint of turpentine and then distilling the same, and removing that fraction boiling above 256 F.

No references cited. 

1. AN INSECTIDAL COMPOSITION COMPRISING: A VEHICLE, A BAIT, AN ATTRACTANT AND A POISON OBTAINED BY ADDING TO 1 GALLON OF THE DISTILLATE BOILING BETWEEN 355 AND 360*F., OBTAINED BY THE DESTRUCTIVE DISTILLATION OF GILSONITE, ADDING 20 OUNCES OF XYLENE, 7 OUNCES OF TRIETHYLOLAMINE AND 1 POUND OF SILICON DIOXIDE, HEATING UNDER PRESSURE TO 300* F. AND COOLING, ADDING 1 GALLON DISTILLED WATER AND 1 PINT OF TURPENTINE AND THEN DISTILLING THE SAME AND REMOVING THAT FRACTION BOILING ABOVE 256*F. 